Hydraulic fracturing is a method of using pump rate and hydraulic pressure to fracture or crack a subterranean formation. Once the crack or cracks are made, high permeability proppant, relative to the formation permeability, is pumped into the fracture to prop open the crack. When the applied pump rates and pressures are reduced or removed from the formation, the crack or fracture cannot close or heal completely because the high permeability proppant keeps the crack open. The propped crack or fracture provides a high permeability path connecting the producing wellbore to a larger formation area to enhance the production of hydrocarbons.
The development of suitable fracturing fluids is a complex art because the fluids must simultaneously meet a number of conditions. For example, they must be stable at high temperatures and/or high pump rates and shear rates that can cause the fluids to degrade and prematurely settle out the proppant before the fracturing operation is complete. Various fluids have been developed, but most commercially used fracturing fluids are aqueous based liquids that have either been gelled or foamed. When the fluids are gelled, typically a polymeric gelling agent, such as a solvatable polysaccharide is used. The thickened or gelled fluid helps keep the proppants within the fluid. Gelling can be accomplished or improved by the use of crosslinking agents or crosslinkers that promote crosslinking of the polymers together, thereby increasing the viscosity of the fluid.
The recovery of fracturing fluids may be accomplished by reducing the viscosity of the fluid to a low value so that it may flow naturally from the formation under the influence of formation fluids. Crosslinked gels generally require viscosity breakers to be injected to reduce the viscosity or “break” the gel. Enzymes, oxidizers, and acids are known polymer viscosity breakers. Enzymes are effective within a pH range, typically a 2.0 to 10.0 range, with increasing activity as the pH is lowered towards neutral from a pH of 10.0. Most conventional borate crosslinked fracturing fluids and breakers are designed from a fixed high crosslinked fluid pH value at ambient temperature and/or reservoir temperature. Optimizing the pH for a borate crosslinked gel is important to achieve proper crosslink stability and controlled enzyme breaker activity.
One difficulty with conventional fracturing fluids is the fact that they tend to emulsify when they come into contact with crude oil. Emulsions with crude oil can impair to totally restrict reservoir production. In order to prevent potential fracturing fluid-crude oil emulsions a demulsifier additive is used. Demulsifiers are typically used from 0.1 to 0.5% by volume within the fracturing fluid. Examples of demulsifier chemicals commonly used include alkyl sulfates, alkyl sulphonates, alkyl aromatic sulphonates, ethoxylated alkyl sulphonates, alkyl phosphonates, alkyl quaternary amines, alkyl amine oxides, oxyalkylated polyalkylene poly-amines, fatty acid polyalkyl aromatic ammonium chloride, polyalkylene glycols, polyalkylene glycol ethers, alkyl acrylates, alkyl amino alkyl acrylates, polyacrylates, alkyl acrylamides, alkyl amino alkyl acrylamides, polyacrylamides, alkyl phenols, ethoxylated alkyl phenol, polyoxyalkylated alkyl phenol resin, polyalkyl resins, alkyl phenol resins, alkyl phenol-aldehyde resins, alkoxylated alkyl phenol-aldehyde resins, polyoxylated alkyl phenol-aldehyde condensates, oligoamine alkoxylates, alkoxylated carboxylic acid esters, ethoxylated alcohols, organic and inorganic aluminum salts, copolymers of acrylates-surfactants, copolymers of acrylates-resins, copolymers of acrylates-alkyl aromatic amines, copolymers of carboxylics-polyols, co- or terpolymers of alkoxylated acrylates or methacrylates with vinyl compounds, condensates of mono- or oligoamine alkoxylates, dicarboxylic acids and alkylene oxide block copolymers, or blends of various demulsifier substances. Further, certain chemicals are known to enhance the performance of demulsifiers. Various demulsifier enhancers include, but are not necessarily limited to the following: alcohols, aromatics, alkanolamines, carboxylic acids, amino carboxylic acids, bisulfites, hydroxides, sulfates, phosphates, polyols, and mixtures thereof.
Fracturing fluids also include additives to help inhibit the formation of scale including, but not necessarily limited to, carbonate scales and sulfate scales. Such scale cause blockages not only in the equipment used in hydrocarbon recovery, but also can create fines that block the pores of the subterranean formation. Examples of scale inhibitors and/or scale removers incorporated into fracturing fluids include, but are not necessarily limited to polyaspartates; hydroxyaminocarboxylic acid (HACA) chelating agents, such as hydroxyethyliminodiacetic acid (HEIDA); ethylenediaminetetracetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), nitrilotriacetic acid (NTA) and other carboxylic acids and their salt forms, phosphonates, acrylates, and acrylamides, and mixtures thereof.
Fracturing fluids that are crosslinked with titanate, zirconate, and/or borate ions (using compounds which generate these ions), sometimes contain additives that are designed to delay crosslinking. Crosslinking delay agents permit the fracturing to be pumped down hole to the subterranean formation before crosslinking begins to occur, thereby permitting more versatility or flexibility in the fracturing fluid. Examples of crosslink delay agents commonly incorporated into fracturing fluids include, but are not necessarily limited to organic polyols, such as sodium gluconate; sodium glucoheptonate, sorbitol, glyoxal, mannitol, phosphonates, aminocarboxylic acids and their salts (EDTA, DTPA, etc.) and mixtures thereof.
Other common additives employed in conventional fracturing fluids include crosslinked gel stabilizers that stabilize the crosslinked get (typically a polysaccharide crosslinked with titanate, zirconate or borate) for a sufficient period of time so that the pump rate and hydraulic pressure may fracture the subterranean formations. Suitable crosslinked gel stabilizers previously used include, but are not necessarily limited to, sodium thiosulfate, diethanolamine, triethanolamine, methanol, hydroxyethylglycine, tetraethylenepentamine, ethylenediamine and mixtures thereof.
Additional common additives for fracturing fluids are enzyme breaker (protein) stabilizers. These compounds stabilize the enzymes and/or proteins used in the fracturing fluids to eventually break the gel after the subterranean formation is fractured so that they are still effective at the time it is desired to break the gel. If the enzymes degrade too early they will not be available to effectively break the gel at the appropriate time. Examples of enzyme breaker stabilizers commonly incorporated into fracturing fluids include polyols (such as sorbitol, mannitol, and glycerol), sugars (such as lactose, fructose, and sucrose), inorganic salts (such as sodium chloride, potassium chloride, and calcium chloride), borax, boric acid, sulfites, erythorbates, polycarboxylic acids and their salts (such as oxalic acid, maleic acid, succinic acid, tartaric acid, aspartic acid, and citric acid), amino acids (such as arginine, lysine, glycine, and glutamine), aminocarboxylic acids and their salts (such as EDTA, DTPA, NTA), phosphates, phosphonates, sulfates, sulphonates, acrylates, acrylamides, and mixtures thereof.
Further, many of the common additives previously used discussed above present environmental concerns because they are not readily biodegradable when it becomes necessary to dispose of the fracturing fluid.
It would be desirable if multifunctional fracturing fluid compositions could be devised that have suitable properties or characteristics as discussed above using biodegradable additives and compounds.